EP1629043A1 - Composition de fluoroelastomere presentant d'excellentes proprietes a basse temperature - Google Patents

Composition de fluoroelastomere presentant d'excellentes proprietes a basse temperature

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Publication number
EP1629043A1
EP1629043A1 EP04753269A EP04753269A EP1629043A1 EP 1629043 A1 EP1629043 A1 EP 1629043A1 EP 04753269 A EP04753269 A EP 04753269A EP 04753269 A EP04753269 A EP 04753269A EP 1629043 A1 EP1629043 A1 EP 1629043A1
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EP
European Patent Office
Prior art keywords
group
curable composition
tetrafluoroethylene
perfluoro
fluoroelastomer
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Granted
Application number
EP04753269A
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German (de)
English (en)
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EP1629043B1 (fr
Inventor
Ming-Hong Hung
Walter Werner Schmiegel
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DuPont Performance Elastomers LLC
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DuPont Dow Elastomers LLC
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • This invention relates to fluoroelastomer compositions, and in particular to the enhancement of the low temperature properties of such compositions.
  • Elastomeric fluoropolymers exhibit excellent resistance to the effects of heat, weather, oil, solvents and chemicals. Such materials are commercially available and are most commonly copolymers of vinylidene fluoride (VF 2 ) with hexafluoropropylene (HFP) and, optionally, tetrafluoroethylene (TFE).
  • VF 2 vinylidene fluoride
  • HFP hexafluoropropylene
  • TFE tetrafluoroethylene
  • Other known fluoroelastomers include copolymers of TFE with a perfluoro(alkyl vinyl ether) such as perfluoro(methyI vinyl ether) (PMVE), copolymer of TFE with propylene (P) and, optionally VF 2 , and copolymers of ethylene (E) with TFE and PMVE.
  • these fluoroelastomers also contain copolymerized units of a cure site monomer to facilitate vulcanization. While these copolymers have many desirable properties, including low compression set and excellent processability, their low temperature flexibility is not adequate for all end use applications. One particularly desirable improvement would be a reduction in glass transition temperature (T g ) with an accompanying extension of service temperature to lower temperatures. T g is often used as an indicator of low temperature flexibility because polymers having low glass transition temperatures maintain elastomeric properties at low temperatures.
  • U.S. Patent No. 4,894,418 discloses vinylidene fluoride based fluoroelastomer compositions which contain processing adjuvants that are perfluorinated polyethers having an hydroxyl group at one or both chain ends. Among the benefits listed for such adjuvants is improved low temperature properties. Being perfluorinated, the polyethers disclosed in the '418 patent are not very compatible with vinylidene fluoride based fluoroelastomers which contain polar hydrogen atoms. Such incompatibility may cause processability problems and lead to the ready extraction of the polyether by solvents.
  • U.S. Patent No. 5,268,405 discloses compositions of TFE/PMVE copolymers which also contain a perfluoropolyether (e.g. DuPont's Krytox® fluorinated oil) for reducing the T g of the composition.
  • a perfluoropolyether e.g. DuPont's Krytox® fluorinated oil
  • the perfluoropolyethers employed in all the above compositions tend to be fugitive.
  • the level of perfluoropolyether in the compositions decreases, the physical properties of the compositions revert to those of compositions containing no perfluoropolyether.
  • the present invention is directed to a curable composition
  • a curable composition comprising
  • A a fluoroelastomer copolymer
  • a fluorinated polyether having a general formula of — [CF 2 CFH- 0-Rf-CF 2 CH 2 O] n — , wherein n is such that M w is between 2000 and 100,000 and R f is selected from the group consisting of a) — (CF 2 ) S — , wherein s is 1 to 10 ; and b)
  • the fluoroelastomers employed in the compositions of the present invention are capable of undergoing crosslinking reactions with any of the known curatives for fluoroelastomers such as, but not limited to polyhydroxy compounds such as bisphenol AF, diamines such as 1 ,6- hexamethylenediamine or its dicarbamate, the combination of organic peroxides and polyfunctional coagents, organotin (U.S. Patent No. 5,789,489), bis(aminophenols) such as diaminobisphenol AF (U.S. Patent No.
  • the resulting cured elastomeric compositions exhibit good low temperature properties without the loss of other important properties such as tensile strength and compression set resistance.
  • the fluorinated polyethers employed in the compositions of the invention are relatively compatible with the fluoroelastomer and stable to heat. The polyethers do not volatilize out of the crosslinked compositions at typical service temperatures (i.e. 250°- 270°C).
  • fluoroelastomer which may be employed in the compositions of this invention is based on vinylidene fluoride (VF 2 ).
  • this type of fluoroelastomer contains copolymerized units of at least one other fluorine-containing monomer.
  • monomers include, but are not limited to hexafluoropropylene (HFP), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), fluorinated vinyl ethers (FVE) and perfluoro(alkyl vinyl) ethers (PAVE) such as perfluoro(methyl vinyl ether).
  • the fluoroelastomers may optionally contain copolymerized units of methyl vinyl ether, or an olefin such as ethylene (E) or propylene (P).
  • Peroxide curable fluoroelastomers which contain copolymerized units of vinylidene fluoride, perfluoro(methyl vinyl ether) and tetrafluoroethylene are especially preferred.
  • Another type of fluoroelastomer which may be employed in this invention is based on tetrafluoroethylene (TFE). In addition to copolymerized units of TFE, this type of fluoroelastomer contains copolymerized units of at least one other monomer such as a PAVE, a FVE, methyl vinyl ether, E, or P.
  • Fluorinated vinyl ethers (FVE) suitable for use as monomers in the fluoroelastomers employed in this invention include those of the formula
  • CF 2 CFO-(CF 2 ) m -(CH 2 ) n -[O(CF 2 ) ⁇ ] y -O-A
  • m is an integer between 0 and 4
  • n is an integer between 0 and 2
  • x is an integer between 1 and 3
  • y is an integer between 0 and 6
  • A is selected from the group consisting of C- ⁇ -C 4 perfluoroalkyl groups, C-i-C ⁇ perfluoroalkoxy groups, and C 1 -C 4 alkyl groups containing between 0 and 8 fluorine atoms.
  • Perfluoro(alkyl vinyl ethers) (PAVE) suitable for use as monomers include those of the formula
  • CF 2 CFO(RfO) n (RrO) m Rf (I) where R f and R f , are different linear or branched perfluoroalkylene groups of 2-6 carbon atoms, m and n are independently 0-10, and R f is a perfluoroalkyl group of 1-6 carbon atoms.
  • a preferred class of perfluoro(alkyl vinyl ethers) includes compositions of the formula
  • CF 2 CFO(CF 2 CFXO) n R f (II) where X is F or CF3, n is 0-5, and Rf is a perfluoroalkyl group of 1-6 carbon atoms.
  • a most preferred class of perfluoro(alkyl vinyl ethers) includes those ethers wherein n is 0 or 1 and R f contains 1-3 carbon atoms. Examples of such perfluorinated ethers include perfluoro(methyl vinyl ether) (PMVE) and perfluoro(propyl vinyl ether) (PPVE).
  • Additional perfluoro(alkyl vinyl ether) monomers include compounds of the formula
  • the fluoroelastomers employed in the compositions of this invention may also contain a cure site for facilitating crosslinking. Suitable cure sites for crosslinking by organic peroxide/polyfunctional coagent curing systems include, but are not limited to bromine endgroups, iodine endgroups, or a combination thereof.
  • Such cure sites may be introduced to the fluoroelastomer polymer chain by polymerization in the presence of a bromine- or iodine-containing chain transfer agent (U.S. Patent No. 4,243,770). Cure sites may also be introduced by copolymerization of the fluoroelastomer with cure site monomers that contain a bromine or iodine atom such as fluorinated olefins or fluorinated vinyl ethers. Such cure site monomers are well known in the art (e.g. U.S. Patent Nos. 4,214,060; 5,214,106; and 5,717,036).
  • BTFE bromotrifluoroethylene
  • BTFB 4-bromo-3,3,4,4-tetrafluorobutene-1
  • ITFB 4-iodo-3,3,4,4-tetrafluorobutene-1
  • Bis-olefins may also be employed as cure site monomers in peroxide curable fluoroelastomers (U.S. Patent No.
  • Suitable cure sites for crosslinking by polyhydroxy curing systems include, but are not limited to trifluoroethylene; 3,3,3-trifluoropropene-1 ; 1 ,2,3,3,3-pentafluoropropylene; 1 ,1 ,3,3,3-pentafluoropropylene; 2,3,3,3- tetrafluoropropene.
  • AF, 3,3'-diamonobenzidinene, or ammonia generating curatives include, but are not limited to comonomers such as fluorovinyl ethers or fluoroolefins containing pendent nitrile groups. Examples include perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene) (8-CNVE) and the nitrile- containing cure site monomers disclosed in U.S. Patent No. 6,211 ,319 B1.
  • fluoroelastomers suitable for use in the compositions of this invention include, but are not limited to elastomers comprising copolymerized units selected from the group consisting of a) VF 2 /HFP, b) VF 2 /HFP/TFE, c) VF 2 /PMVE, d) VF 2 /PMVE/TFE, e) VF 2 /TFE/P; f) TFE/P; g) E/TFE/PMVE and h) TFE/PMVE.
  • these elastomers further comprise at least one type of cure site described above.
  • the fluoroelastomers employed in the compositions of this invention further comprise both iodine endgroups and copolymerized units of an iodine-containing cure site monomer.
  • An especially preferred fluoroelastomer comprises copolymerized units of vinylidene fluoride, perfluoro(methyl vinyl ether) tetrafluoroethylene and ITFB. The latter elastomer also contains iodine endgroups.
  • the fluorinated polyethers contained in the compositions of this invention are disclosed in U.S. Patent No. 5,134,211.
  • the polyether consists essentially of the repeat unit
  • n is such that the weight average molecular weight (M w ) is between 2000 and 100,000 (preferably between 15,000 and 45,000) and Rf is selected from the group consisting of a) — (CF 2 ) S — , wherein s is 1 to 10; and b) — [CF 2 CF(CF 3 )O]t(CF 2 )u— , wherein u is 1 to 10 and t is 1 to 20.
  • both t and u are 1 , or s is 1-3.
  • t and u are 1 so that the fluorinated polyether contains the repeat unit
  • fluorinated polyethers have CF 2 CFH-O — as one terminal group and — CH 2 OH as the other terminal group.
  • compositions of this invention contain between 2 and 30 parts by weight fluorinated polyether per 100 parts by weight fluoroelastomer (i.e. 2 to 30 phr - parts per hundred parts rubber). Preferably, compositions contain between 2 and 20 phr fluorinated polyether. As shown in the above structures, the fluorinated polyethers employed in this invention contain polar hydrogen atoms in the repeat units, making this polyether more compatible with vinylidene fluoride based fluoroelastomers than are perfluorinated polyethers.
  • fluorinated polyethers may be made by the catalytic anionic polymerization of 9,9-dihydro-9-hydroxy-perfluoro(3,6-dioxa-5-methyl-1 - nonene) (EVE-OH) as disclosed in U.S. Patent 5,134,211.
  • Suitable catalysts include, but are not limited to cesium carbonate, cesium fluoride, tetraalkylammonium chloride, potassium carbonate, potassium t-butoxide, and tetraphenylphosphonium chloride.
  • EVE-OH is readily prepared (U.S.
  • Patent 4,982,009 by the reduction of methyl perfluoro(5-methyl-4,7-dioxa- 8-nonenoate) (EVE) which is commercially available from DuPont.
  • EVE methyl perfluoro(5-methyl-4,7-dioxa- 8-nonenoate)
  • Sodium borohydride is a preferred reducing agent.
  • the curable compositions of the invention may, optionally, also contain an acid acceptor such as a strongly basic amine (e.g. ProtonSponge®, available from Aldrich), a divalent metal oxide (e.g. magnesium oxide, zinc oxide, calcium oxide, or lead oxide), a divalent metal hydroxide; or a mixture of an oxide and hydroxide.
  • an acid acceptor such as a strongly basic amine (e.g. ProtonSponge®, available from Aldrich), a divalent metal oxide (e.g. magnesium oxide, zinc oxide, calcium oxide, or lead oxide), a divalent metal hydroxide; or a mixture of an oxide and hydroxide.
  • the level of the acid acceptor in the compositions of the invention is generally 1-15 phr, with 2-10 parts being preferred.
  • the compositions of the present invention also contain a curing agent.
  • One preferred curing agent is an organic peroxide/polyfunctional coagent system. Useful organic peroxides are those which generate free radicals
  • a dialkyl peroxide or a bis(dialkyl peroxide) which decomposes at a temperature above 50°C is especially preferred.
  • a ditertiarybutyl peroxide having a tertiary carbon atom attached to a peroxy oxygen is especially preferred.
  • the most useful peroxides of this type are 2,5-dimethyl-2,5- di(tertiarybutylperoxy)hexyne-3 and 2,5-dimethyl-2,5- di(tertiarybutylperoxy)-hexane.
  • peroxides can be selected from such compounds as dicumyl peroxide, dibenzoyl peroxide, tertiarybutyl perbenzoate, and di[1 ,3-dimethyl-3-(t-butylperoxy)butyl]carbonate. Generally, about 1-3 phr peroxide is used.
  • the polyfunctional coagent employed with an organic peroxide is a polyunsatu rated compound that is capable of cooperating with the peroxide to provide a useful cure.
  • These coagents can be added in an amount equal to 0.1 and 10 phr, preferably between 2-5 phr.
  • the coagent may be one or more of the following compounds: triallyl cyanurate; triallyl isocyanurate; tri(methallyl)isocyanurate; tris(diallylamine)-s-triazine; triallyl phosphite; N,N-diallyl acrylamide; hexaallyl phosphoramide; N,N,N',N'- tetraalkyl tetraphthalamide; N,N,N',N'-tetraallyl malonamide; trivinyl isocyanurate; 2,4,6-trivinyl methyltrisiloxane; and tri(5-norbomene-
  • 2-methylenecyanurate Particularly useful is triallyl isocyanurate (TAIC).
  • compositions of the invention may also be cured with a polyhydroxy curing agent.
  • a polyhydroxy curing agent preferably 1-3 parts
  • Such compositions contain between 0.1 to 20 parts by weight (preferably 1-3 parts) of polyhydroxy crosslinking agent (or a derivative thereof) per 100 parts fluoroelastomer.
  • Typical polyhydroxy cross-linking agents include di-, tri-, and tetrahydroxybenzenes, naphthalenes, and anthracenes, and bisphenols of the formula
  • A is a difunctional aliphatic, cycloaliphatic, or aromatic radical of 1- 13 carbon atoms, or a thio, oxy, carbonyl, sulfinyl, or sulfonyl radical; A may optionally be substituted with at least one chlorine or fluorine atom; x is 0 or 1 ; n is 1 or 2; and any aromatic ring of the polyhydroxylic compound may optionally be substituted with at least one chlorine or fluorine atom, an amino group, a -CHO group, or a carboxyl or acyl radical.
  • Preferred polyhydroxy compounds include hexafluoroisopropylidene-bis(4-hydroxy-benzene) (i.e.
  • A is alkylene
  • A when A is alkylene, it can be for example methylene, ethylene, chloroethylene, fluoroethylene, difluoroethylene, propylidene, isopropylidene, tributylidene, heptachlorobutylidene, hepta- fluorobutylidene, pentylidene, hexylidene, and 1 ,1-cyclohexylidene.
  • A When A is a cycloalkylene radical, it can be for example 1 ,4-cyclohexylene, 2- chloro-1 ,4-cyclohexylene, cyclopentylene, or 2-fluoro-1 ,4-cyclohexylene. Further, A can be an arylene radical such as m-phenylene, p-phenylene, o-phenylene, methylphenylene, dimethylphenylene, 1 ,4-naphthylene, 3- fluoro-1 ,4-naphthylene, and 2,6-naphthylene.
  • Additional polyhydroxy curing agents include alkali metal salts of bisphenol anions, quaternary ammonium salts of bisphenol anions, tertiary sulfonium salts of bisphenol anions and quaternary phosphonium salts of bisphenol anions.
  • the salts of bisphenol A and bisphenol AF include the disodium salt of bisphenol AF, the dipotassium salt of bisphenol AF, the monosodium monopotassium salt of bisphenol AF and the benzyltriphenylphosphonium salt of bisphenol AF.
  • Quaternary ammonium and phosphonium salts of bisphenol anions are discussed in U.S. Patents 4,957,975 and 5,648,429.
  • Bisphenol AF salts (1 :1 molar ratio) with quaternary ammonium ions of the formula R ⁇ R 2 R 3 N + , wherein R 1 -R 4 are CrC 8 alkyl groups and at least three of R R 4 are C 3 or C 4 alkyl groups are preferred.
  • Specific examples of these preferred compositions include the 1:1 molar ratio salts of tetrapropyl ammonium-, methyltributylammonium- and tetrabutylammonium bisphenol AF. Such salts may be made by a variety of methods.
  • a methanolic solution of bisphenol AF may be mixed with a methanolic solution of a quaternary ammonium salt, the pH is then raised with sodium methoxide, causing an inorganic sodium salt to precipitate.
  • the tetraalkylammonium/BPAF salt may be isolated from solution by evaporation of the methanol.
  • a methanolic solution of tetraalkylammonium hydroxide may be employed in place of the solution of quaternary ammonium salt, thus eliminating the precipitation of an inorganic salt and the need for its removal prior to evaporation of the solution.
  • Vulcanization accelerators are typically employed in polyhydroxy curable compositions of the invention.
  • Typical accelerators include tertiary sulfonium salts such as [(C 6 H 5 ) 2 S + (C 6 Hi 3 )][CI] " , and
  • R5, ⁇ , R7. and Rs are individually C1-C20 alkyl, aryl, aralkyl, alkenyl, and the chlorine, fluorine, bromine, cyano, -OR, and -COOR substituted analogs thereof, with R being C1-C20 alkyl, aryl, aralkyl, alkenyl, and where X is halide, hydroxide, sulfate, sulfite, carbonate, pentachlorothiophenolate, tetrafluoroborate, hexafluorosilicate, hexafluorophosphate, dimethyl phosphate, and C-i-C ⁇ o alkyl, aryl, aralkyl, and alkenyl carboxylates and dicarboxylates.
  • benzyltri-phenylphosphonium chloride benzyltriphenylphosphonium bromide, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, tributylallylphosphonium chloride, tributyl-2-methoxypropylphosphonium chloride, 1 ,8-diazabicyclo[5.4.0]undec-7-ene, and benzyldiphenyl(dimethylamino) phosphonium chloride.
  • methyltrioctylammonium chloride methyltributylammonium chloride, tetrapropylammonium chloride, benzyltrioctylphosphonium bromide, benzyltrioctylphosphonium chloride, methyltrioctylphosphonium acetate, tetraoctylphosphonium bromide, methyltriphenylarsonium tetrafluoroborate, tetraphenylstibonium bromide, 4-chlorobenzyltriphenyl phosphonium chloride, 8-benzyl-1 ,8- diazabicyclo(5.4.0)-7-undecenonium chloride, diphenylmethyltriphenylphosphonium chloride, allyltriphenyl-phosphonium chloride, tetrabutylphosphonium bromide, m-trifluoromethyl- benzyltrioctylphosphonium chloride
  • the amount of accelerator used is between 0.1 and 20 parts by weight per hundred parts by weight fluoroelastomer. Preferably, 0.5-3.0 phr is used.
  • Other curatives which may be employed in the compositions of the invention include diamines, carbamates thereof, bis(aminophenols) such as diaminobisphenol, tetraamines, organotin and compounds which decompose to produce ammonia at curing temperatures. When present in the compositions of this invention, typically, 0.1 to 7 phr of any one of the latter curatives is employed.
  • additives may be compounded into the fluoroelastomer to optimize various physical properties.
  • additives include carbon black, stabilizers, plasticizers, lubricants, pigments, fillers (e.g. mineral fillers such as silicas, alumina, barium sulfate, titanium dioxide), and processing aids typically utilized in perfluoroelastomer compounding. Any of these additives can be incorporated into the compositions of the present invention, provided the additive has adequate stability for the intended service conditions.
  • Carbon black is used in elastomers as a means to balance modulus, tensile strength, elongation, hardness, abrasion resistance, conductivity, and processability of the compositions. Carbon black is generally useful in amounts of from 5-60 phr.
  • fluoropolymer fillers may be present in the composition. Generally from 1 to 50 phr of a fluoropolymer filler is used, and preferably at least about 5 phr is present.
  • the fluoropolymer filler can be any finely divided, easily dispersed plastic fluoropolymer that is solid at the highest temperature utilized in fabrication and curing of the perfluoroelastomer composition. By solid, it is meant that the fluoroplastic, if partially crystalline, will have a crystalline melting temperature above the processing temperature(s) of the perfluoroelastomer(s). Such finely divided, easily dispersed fluoroplastics are commonly called micropowders or fluoroadditives. Micropowders are ordinarily partially crystalline polymers.
  • the fluorinated polyether, crosslinking agent, and optional other additives are generally incorporated into the polymer by means of an internal mixer or on a rubber mill.
  • the resultant composition is then cured, generally by means of heat and pressure, for example by compression transfer or injection molding.
  • the curable compositions of the present invention are useful in production of gaskets, tubing, seals and other molded components.
  • Such articles are generally produced by molding a compounded formulation of the curable composition with various additives under pressure, curing the part, and then subjecting it to a post cure cycle.
  • the cured compositions have excellent low temperature flexibility and processability as well as excellent thermal stability and chemical resistance. They are particularly useful in applications such as seals and gaskets requiring a good combination of oil resistance, fuel resistance and low temperature flexibility, for example in fuel injection systems, fuel line connector systems and in other seals for high and low temperature automotive uses.
  • cure characteristics were measured using an Alpha Systems model MDR 2000E moving die rheometer (MDR), under the following conditions (ISO 6502): Moving die frequency: 1.66 Hertz Oscillation amplitude: ⁇ 0.5° Temperature: 180°C Sample size: 6 to 10 g Duration: 12 minutes The following cure parameters were recorded:
  • ML minimum torque level, in units of dN-m
  • Delta M difference between maximum and minimum torque, in units of dN-m t s 2: minutes to a 2.26 dNm rise above
  • ML tc50 minutes to 50% of maximum torque tc90: minutes to 90% of maximum torque
  • T 2 modulus at 100% elongation in units of MPa (ISO 37 T2)
  • T B tensile strength in units of MPa (ISO 3 T2)
  • T s tear strength in units of kN/m (ISO 34, Die B)
  • E B elongation at break in units of % (ISO 37 T2)
  • TR-10 temperature of retraction (ISO 2921)
  • a standard test piece of length 50 mm is stretched at room temperature and then cooled in a bath (usually filled with isopropanol) to a temperature of about 10°C less than the T g of the polymer. The test piece is then allowed to retract freely while the test temperature is raised at a rate of 1°C per minute. Readings of the retracted length are taken every 2 minutes until the retraction reaches 75%.
  • TR-10 is the temperature at which a retraction of 10% is achieved. Hardness (Shore A, ISO 868)
  • Compression set of small pip samples (ISO 815) Glass Transition temperature (T g ) was measured by Modulated Differential Scanning Calorimetry (MDSC) at 10 minute heating rate in nitrogen.
  • MDSC Modulated Differential Scanning Calorimetry
  • the fluorinated polyether (FPE-1 ) employed in the examples was prepared by a 2-step process wherein methyl perfluoro(5-methyl-4,7- dioxa-8-nonenoate) (EVE), commercially available from DuPont, was first converted to 9,9-dihydro-9-hydroxy-perfluoro-(3,6-dioxa-5-methyl-1- nonene) (EVE-OH) and then the EVE-OH was homopolymerized.
  • EVE methyl perfluoro(5-methyl-4,7- dioxa-8-nonenoate)
  • EVE-OH 9,9-dihydro-9-hydroxy-perfluoro-(3,6-dioxa-5-methyl-1- nonene)
  • TGA Thermal gravimetric analysis
  • the fluoroelastomers employed in the Examples were FE-1 : an iodine-containing copolymer of vinylidene fluoride, perfluoro(methyl vinyl ether), and tetrafluoroethylene, commercially available from DuPont Dow Elastomers as Viton® GBLT-S.
  • FE-2 a copolymer of ethylene, tetrafluoroethylene and perfluoro(methyl vinyl ether) having iodine and bromine cure sites, commercially available from DuPont Dow Elastomers as Viton® ETP-S.
  • FE-3 a copolymer of vinylidene fluoride and hexafluoropropylene also containing bisphenol AF curative, commercially available from DuPont Dow Elastomers as Viton® A201 C.
  • FE-4 a copolymer of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene also containing bisphenol AF curative, commercially available from DuPont Dow Elastomers as Viton® B601C.
  • compositions of the invention (Examples 1-5) and control compositions (Comparative Examples A and B), not containing a fluorinated polyether, were made by compounding the ingredients in a conventional manner on a 2-roll mill. The ingredients and proportions are shown in Table I.
  • Fluorinated Polyether FPE-1 0 5 10 20 15 20 0
  • Fluoroelastomer FE-1 100 100 100 100 10 100 100 100 0
  • composition of the invention (Example 6) and control composition (Comparative Example C), not containing a fluorinated polyether, were made by compounding the ingredients in a conventional manner on a 2- roll mill. The ingredients and proportions are shown in Table V.
  • compositions of the invention (Examples 7 and 8) and control compositions (Comparative Example D and E), not containing a fluorinated polyether, were made by compounding the ingredients in a conventional manner on a 2-roll mill. The ingredients and proportions are shown in Table VII.
  • Fluoroelastomer FE-3 100 100 0 0 Fluoroelastomer FE-4 0 0 100 100 MT Carbon Black 1 45 45 45 45 Flunace Carbon Black 2 10 10 10 10 10 Magnesium Oxide 3 3 3 3 Calcium Hydroxide 4 1.6 1.6 1.6 1.6 1.6
  • Thermax Floform N990 (available from Lehmann & Voss Co.)
  • Rhenofit CF available from Rhein Chemie Rheinau GmbH, Germany
  • Example Example 7 Comp. Ex. D
  • Example 8 Comp. Ex. E

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  • Polymers & Plastics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des compositions contenant des fluoroélastomères, un vulcanisant et un polyéther fluoré de la formule générale -[CF2CFH-O-RfCF2CH2O]n-, dans laquelle n est tel que la masse moléculaire moyenne en poids, Mw, est comprise entre 2000 et 100000 et Rf est choisi dans le groupe constitué de a) -(CF2)s-, où s est compris entre 1 et 10; et b) -[CF2CF(CF3)O]t(CF2)u-, où u est compris entre 1 et 10 et t est compris entre 1 et 20, lesdites compositions présentant d'excellentes propriétés à basse température.
EP04753269A 2003-05-21 2004-05-19 Composition de fluoroelastomere presentant d'excellentes proprietes a basse temperature Expired - Lifetime EP1629043B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US47223203P 2003-05-21 2003-05-21
US10/800,893 US20040236028A1 (en) 2003-05-21 2004-03-15 Fluoroelastomer composition having excellent low temperature properties
PCT/US2004/016411 WO2004104092A1 (fr) 2003-05-21 2004-05-19 Composition de fluoroelastomere presentant d'excellentes proprietes a basse temperature

Publications (2)

Publication Number Publication Date
EP1629043A1 true EP1629043A1 (fr) 2006-03-01
EP1629043B1 EP1629043B1 (fr) 2006-08-09

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Family Applications (1)

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EP04753269A Expired - Lifetime EP1629043B1 (fr) 2003-05-21 2004-05-19 Composition de fluoroelastomere presentant d'excellentes proprietes a basse temperature

Country Status (5)

Country Link
US (1) US20040236028A1 (fr)
EP (1) EP1629043B1 (fr)
JP (1) JP4455596B2 (fr)
DE (1) DE602004001879T2 (fr)
WO (1) WO2004104092A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060270780A1 (en) * 2005-05-25 2006-11-30 Ping Xu High purity perfluoroelastomer composites and a processes to produce the same
EP2277962B1 (fr) * 2008-04-30 2013-07-10 DIC Corporation Composition de revêtement durcissable par un rayonnement d'énergie active, produit durci de celle-ci et nouvelle résine durcissable
EP2294121B1 (fr) * 2008-06-30 2018-10-17 Daikin Industries, Ltd. Composition durcissable et article moulé fait de cette composition
KR101853987B1 (ko) * 2010-07-14 2018-05-02 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. 플루오로 엘라스토머 조성물
CN102558719B (zh) * 2011-12-29 2014-07-02 中昊晨光化工研究院 一种耐低温含氟弹性体及其制备方法
JP6910306B2 (ja) * 2015-05-29 2021-07-28 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． フルオロエラストマー組成物
EP3408320A1 (fr) * 2016-01-26 2018-12-05 E. I. du Pont de Nemours and Company Composés fluoroélastomère
CN108884198A (zh) * 2016-03-11 2018-11-23 索尔维特殊聚合物意大利有限公司 用于固化氟弹性体组合物的多不饱和化合物
JP7005590B2 (ja) * 2016-07-18 2022-01-21 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． フルオロエラストマー組成物
US10899917B2 (en) * 2016-10-27 2021-01-26 Solvay Specialty Polymers Italy S.P.A. Fluoroelastomer composition

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1199986B (it) * 1982-07-07 1989-01-05 Montedison Spa Composizioni convulcanizzabili a base di fluoroelastomeri e composti polimerici a struttura perfluoropolieterea
IT1200801B (it) * 1985-10-17 1989-01-27 Ausimont Spa Addittivi coadiuvanti di lavorazione per gomme vulcannizzabilli mediante perossidi
IT1209669B (it) * 1985-11-15 1989-08-30 Ausimont Spa Composizioni vulcanizzabili fluoroelastomeri aventi migliorate caratteristiche di processabilita'e di stabilita' chimica.
IT1222804B (it) * 1987-10-02 1990-09-12 Ausimont Spa Additivi coadiuvanti al distacco degli stampi di gomme vulcanizzabili mediante perossidi
US5134211A (en) * 1990-01-31 1992-07-28 E. I. Du Pont De Nemours And Company Hydroxy containing fluorovinyl compounds and polymers thereof
US4982009A (en) * 1990-01-31 1991-01-01 E. I. Du Pont De Nemours And Company Hydroxy containing fluorovinyl compounds and polymers thereof
DE69233097T2 (de) * 1991-01-11 2004-05-06 Dyneon Llc, Oakdale Fluorelastomerzusammensetzung
US5268405A (en) * 1993-03-31 1993-12-07 E. I. Du Pont De Nemours And Company Low temperature perfluoroelastomers
IT1282390B1 (it) * 1996-05-02 1998-03-20 Ausimont Spa Composizioni vulcanizzabili di fluoroelastomeri
US5681881A (en) * 1996-05-24 1997-10-28 Minnesota Mining And Manufacturing Company Fluoroelastomer compositions
IT1283136B1 (it) * 1996-07-09 1998-04-07 Ausimont Spa Lattici acquosi a base di fluoropolimeri
IT1318388B1 (it) * 2000-03-14 2003-08-25 Ausimont Spa Composizioni lubrificanti a base di ptfe.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004104092A1 *

Also Published As

Publication number Publication date
US20040236028A1 (en) 2004-11-25
DE602004001879T2 (de) 2007-03-29
JP2006528728A (ja) 2006-12-21
WO2004104092A1 (fr) 2004-12-02
DE602004001879D1 (de) 2006-09-21
JP4455596B2 (ja) 2010-04-21
EP1629043B1 (fr) 2006-08-09

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